CN101898159A - Mixed resin and preparation method thereof - Google Patents
Mixed resin and preparation method thereof Download PDFInfo
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- CN101898159A CN101898159A CN 201010238540 CN201010238540A CN101898159A CN 101898159 A CN101898159 A CN 101898159A CN 201010238540 CN201010238540 CN 201010238540 CN 201010238540 A CN201010238540 A CN 201010238540A CN 101898159 A CN101898159 A CN 101898159A
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- ion exchange
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- 239000011347 resin Substances 0.000 title claims abstract description 106
- 229920005989 resin Polymers 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title abstract description 51
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 323
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 323
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 323
- 238000005342 ion exchange Methods 0.000 claims description 98
- 238000000034 method Methods 0.000 claims description 24
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 96
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000002411 adverse Effects 0.000 abstract 1
- 239000000498 cooling water Substances 0.000 description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000007599 discharging Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000010612 desalination reaction Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 238000005352 clarification Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- JSAIENUMNDAGTD-UHFFFAOYSA-N benzene ethene styrene Chemical compound C1=CC=CC=C1.C=C.C=C.C=CC1=CC=CC=C1 JSAIENUMNDAGTD-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 108020004999 messenger RNA Proteins 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention relates to a mixed resin, comprising OH-type ion exchange resin, Na-type ion exchange resin and H-type ion exchange resin, wherein the OH-type ion exchange resin, the Na-type ion exchange resin and the H-type ion exchange resin are gel-type ion exchange resin. The invention also provides a preparation method thereof, comprising the step of mixing the OH-type ion exchange resin, the Na-type ion exchange resin and the H-type ion exchange resin. The mixed resin is used for treating cold water in a generator to keep the pH value of the cold water above 7.5 for long time, and bring no adverse impact to the conductivity of the cold water and no corrosion to the inner parts of the generator.
Description
Technical field
The present invention relates to a kind of hybrid resin and preparation method thereof.
Background technology
Generator is transformed into heat energy owing to energy consumption with portion of energy in operation process, make the temperature of parts such as rotor, stator raise, and then the winding that causes insulating is aging, the decline of exerting oneself, even burn motor.Therefore, be necessary the parts in the generator are cooled off.But, because electric generator inner cooling water is to work under the environment of high voltage electric field, therefore, to compare with common cooling water, electric generator inner cooling water also should have good electrical insulation properties except the requirement that will satisfy burn into non-scaling not.Yet the oxygen in the generator cooling-water course of work in the inevitable meeting dissolved air, carbon dioxide etc. make the pH value of electric generator inner cooling water reduce gradually, and then corrode inner initiation of generator.Therefore, requiring the dissolved oxygen in the electric generator inner cooling water usually is≤80 μ g/L, and the pH value is 〉=7.0, and electrical conductivity is≤2.0 μ S/cm; From the angle of safety, in actual moving process, power plant is controlled to be the pH value of electric generator inner cooling water usually 〉=and 7.5, electrical conductivity is controlled to be≤1.5 μ S/cm.
In order to reduce the amount of dissolved oxygen in the electric generator inner cooling water, the pH value of electric generator inner cooling water is controlled to be is not less than 7.5, and then prevent that the internal part corrosion of generator, power plant from using condensate water that water vapor condensation forms the later on inner cold water as generator usually.But, because condensate water is regulated the pH value by adding ammonia, therefore, when the pH of condensate water value is higher (, when the ammonia content in the condensate water is higher), can cause electric conductivity of inside cold water to exceed standard on the one hand; On the other hand, because the material of the stator bar of generator inside is generally copper, and copper is very responsive to ammonia, therefore very easily causes the corrosion of copper.
To sum up, how well the pH value of electric generator inner cooling water is controlled to be and is not less than 7.5, can not significantly improve the electrical conductivity of electric generator inner cooling water again, also can not produce corrosion simultaneously and remain a problem demanding prompt solution the generator internal part.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of hybrid resin is provided, this hybrid resin not only can be for a long time be controlled to be the pH value of electric generator inner cooling water more than 7.5, and can the electrical conductivity of electric generator inner cooling water not had a negative impact, the electrical conductivity of electric generator inner cooling water can be controlled to be and not be higher than 1.5 μ S/cm, also can not produce corrosion simultaneously the internal part of generator.
The invention provides a kind of hybrid resin, wherein, this hybrid resin contains OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, and described OH type ion exchange resin, Na type ion exchange resin and the H type ion exchange resin gel-type ion-exchange resin of respectively doing for oneself.
The present invention also provides the method for preparing described hybrid resin, wherein, this method comprises mixes OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, and described OH type ion exchange resin, Na type ion exchange resin and the H type ion exchange resin gel-type ion-exchange resin of respectively doing for oneself.
Hybrid resin provided by the invention contains OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin simultaneously.In the generator operation process, above-mentioned three kinds of ion exchange resin can be respectively with electric generator inner cooling water in ion following reaction takes place:
nRH+A
n+＝R
nA+nH
+，
mRNa+A
m+＝R
mA+mNa
+，
kR′OH+B
k-＝R′
kB+kOH
-。
The product of above-mentioned ion-exchange reactions can continue to take place following reaction, finally generates water and NaOH, thereby prevents that the prolongation pH value with the generator operation time reduces electric generator inner cooling water gradually owing to dissolved oxygen, carbon dioxide etc.,
H
++OH
-＝H
2O，
Na
++OH
-＝NaOH。
Preparation method according to hybrid resin of the present invention is simple and easy to do, and is workable.
Adopt the hybrid resin according to the present invention of method preparation provided by the invention that electric generator inner cooling water is handled, can remain the pH value of electric generator inner cooling water more than 7.5 for a long time on the one hand, also can the electrical conductivity of electric generator inner cooling water not had a negative impact on the other hand, can be for a long time the electrical conductivity of electric generator inner cooling water be remained below the 1.5 μ S/cm, also can not corrode the internal part of generator simultaneously.
The specific embodiment
The invention provides a kind of hybrid resin, wherein, this hybrid resin contains OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, and described OH type ion exchange resin, Na type ion exchange resin and the H type ion exchange resin gel-type ion-exchange resin of respectively doing for oneself.
According to hybrid resin of the present invention, this hybrid resin contains OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, and above-mentioned three kinds of ion exchange resin act synergistically, and can significantly improve the pH value of electric generator inner cooling water.Wherein, described OH type ion exchange resin can with the anion generation ion-exchange reactions in the electric generator inner cooling water, Na type ion exchange resin and H type ion exchange resin then can be respectively with electric generator inner cooling water in cation generation ion-exchange reactions, further reaction between the product of above-mentioned ion-exchange reactions, thereby the final NaOH that generates in electric generator inner cooling water has avoided electric generator inner cooling water in the course of the work owing to the pH value that dissolved oxygen, carbon dioxide etc. causes reduces.
According to hybrid resin of the present invention, described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin are preferably gel-type ion-exchange resin separately.Adopt gel-type ion-exchange resin can be better with electric generator inner cooling water in inorganic ions carry out ion-exchange, and then better the pH of electric generator inner cooling water is remained more than 7.5, and can the electrical conductivity of electric generator inner cooling water not had a negative impact, the electrical conductivity of electric generator inner cooling water can be remained and be not higher than 1.5 μ S/cm.Among the present invention, described gel-type ion-exchange resin is meant that inside does not have pore under dry situation, and swollen when suction is at the ion exchange resin of the very fine hole of macromolecular chain internode formation.
The present invention is not particularly limited for the matrix resin of described gel-type ion-exchange resin.Preferably, described gel-type ion-exchange resin is the polystyrene gel-type ion-exchange resin.For example, the matrix resin of described polystyrene gel-type ion-exchange resin can be styrene diethylene benzene copoly mer, and the degree of cross linking of this copolymer can be 4-8 mole %.
Mol ratio according to the ion-exchange group in the OH type ion exchange resin in the hybrid resin of the present invention, ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin can be in very big range.The present inventor finds in experimentation, ion-exchange group in described OH type ion exchange resin, the mol ratio of the ion-exchange group in ion-exchange group in the Na type ion exchange resin and the H type ion exchange resin is 1: 0.1-0.8: 0.08-0.75, and described OH type ion exchange resin, when Na type ion exchange resin and H type ion exchange resin are respectively done for oneself gel-type ion-exchange resin, not only can make the pH value of electric generator inner cooling water remain more than 7.5 for a long time, and can the electrical conductivity of electric generator inner cooling water not had a negative impact, electrical conductivity can be remained below the 0.5 μ S/cm.
More preferably, the mol ratio of the ion-exchange group in the described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is 1: 0.4-0.75: 0.1-0.45.The mol ratio of the ion-exchange group in described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is within the above-mentioned scope, and when described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin are respectively done for oneself gel-type ion-exchange resin, the pH value of electric generator inner cooling water can be remained for a long time more than 7.5, the electrical conductivity of electric generator inner cooling water is remained below the 0.3 μ S/cm.
Further preferably, the mol ratio of ion-exchange group, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin in the described OH type ion exchange resin is 1: 0.65-0.75: 0.1-0.2.The mol ratio of the ion-exchange group in described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is within the above-mentioned scope, and when described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin are respectively done for oneself gel-type ion-exchange resin, the pH value of electric generator inner cooling water can be remained on for a long time in the scope of 7.7-8.5, the electrical conductivity of electric generator inner cooling water is remained between the 0.1-0.3 μ S/cm.
Most preferably, the mol ratio of the ion-exchange group in the described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is 1: 0.65-0.7: 0.15-0.2.The mol ratio of the ion-exchange group in described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is within the above-mentioned scope, and when described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin are respectively done for oneself gel-type ion-exchange resin, the pH value of electric generator inner cooling water can be remained for a long time more than 8.5, the electrical conductivity of electric generator inner cooling water is remained about 0.27 μ S/cm.
Among the present invention, the quantity of ion-exchange group is meant the quantity that can carry out the ion-exchange group of ion-exchange in the ion exchange resin, can calculate by following formula:
The volume of the operating capacity * ion exchange resin of the quantity of ion-exchange group (mole)=ion exchange resin.
Among the present invention, described operating capacity is meant the molal quantity according to the ion-exchange group that ion exchange resin contained of the unit volume of the condition of work of DL/T772-2001 regulation and method of testing mensuration.
The operating capacity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin is not particularly limited.For example, the operating capacity of described OH type ion exchange resin can for the 450-600 mM/liter, the operating capacity of described Na type ion exchange resin and H type ion exchange resin can respectively do for oneself the 950-1010 mM/liter.Because Na type ion exchange resin can obtain by H type ion exchange resin is made the transition, therefore the operating capacity of described Na type ion exchange resin can be identical with described H type ion exchange resin.The ion exchange resin that operating capacity is in the above-mentioned scope can be commercially available, and for example: described OH type ion exchange resin can be the gel-type ion-exchange resin acquisition of 550A by being purchased from the trade mark of DOW Chemical; Described H type ion exchange resin and Na type ion exchange resin can be the gel-type ion-exchange resin acquisition of 650C by being purchased from the model of DOW Chemical.
The present invention is not particularly limited the content of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, can carry out suitable selection according to the mol ratio of the ion-exchange group of ion-exchange group in the ion-exchange group in the OH type ion exchange resin in the hybrid resin, the Na type ion exchange resin and H type ion exchange resin and the operating capacity of above-mentioned three kinds of ion exchange resin, not repeat them here.
According to hybrid resin of the present invention, the rate of small round spheres of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin is not particularly limited.From the angle of the mechanical strength of further raising ion exchange resin, the rate of small round spheres of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin is preferably more than 95% separately.Among the present invention, the coefficient of uniformity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin can be 1.05-1.60 separately, is preferably 1.05-1.40.Among the present invention, described rate of small round spheres is meant that resin is the percentage that the spherical particle number accounts for total number of particles; Described coefficient of uniformity is meant can be by the sieve diameter of 60% volume of resins and the ratio of the sieve diameter of the resin that can pass through 10% volume.
Among the present invention, the ion-exchange group of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin can suitably be selected according to concrete service condition, is not particularly limited.
Particularly, the ion-exchange group of described OH type ion exchange resin can be quaternary ammonium group, is preferably-N (CH
3)
3OH; The ion-exchange group of described Na type ion exchange resin is preferably-SO
3Na; The ion-exchange group of described H type ion exchange resin is preferably-SO
3The H group.
The present invention also provides a kind of method for preparing described hybrid resin, this method comprises mixes OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, and described OH type ion exchange resin, Na type ion exchange resin and the H type ion exchange resin gel-type ion-exchange resin of respectively doing for oneself.
According to the method for the described hybrid resin of preparation of the present invention, described gel-type ion-exchange resin is preferably the gel-type styrene ion exchange resin.
Volume ratio between the operating capacity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin and OH type ion exchange resin, Na type ion exchange resin and the H type ion exchange resin is not particularly limited.
Preferably, the volume ratio of the operating capacity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin and described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin makes that the mol ratio of ion-exchange group, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin in the described OH type ion exchange resin is 1: 0.1-0.8: 0.08-0.75.
More preferably, the volume ratio of the operating capacity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin and described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin makes that the mol ratio of ion-exchange group, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin in the described OH type ion exchange resin is 1: 0.4-0.75: 0.1-0.45.
Further preferably, the volume ratio of the operating capacity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin and described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin makes that the mol ratio of ion-exchange group, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin in the described OH type ion exchange resin is 1: 0.65-0.75: 0.1-0.2.
Most preferably, the volume ratio of the operating capacity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin and described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin makes that the mol ratio of ion-exchange group, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin in the described OH type ion exchange resin is 1: 0.65-0.7: 0.15-0.2.
Usually, the operating capacity of described OH type ion exchange resin can for the 450-600 mM/liter, the operating capacity of described Na type ion exchange resin and H type ion exchange resin separately can for the 950-1010 mM/liter.
The ion-exchange group of described OH type ion exchange resin can be quaternary ammonium group, is preferably-N (CH
3)
3OH; The ion-exchange group of described Na type ion exchange resin is preferably-SO
3Na; The ion-exchange group of described H type ion exchange resin is preferably-SO
3The H group.
According to hybrid resin of the present invention, described OH type ion exchange resin, H type ion exchange resin and Na type ion exchange resin preferably carry out preliminary treatment before use, to remove mechanical admixture and the residual organic that contains in the ion exchange resin, simultaneously all right activating ion exchanger resin is with the ion-exchange group type of transition for needing of ion exchange resin.The present invention is not particularly limited for described pretreated method, employing well known to a person skilled in the art that method (for example: embodiments of the invention and Comparative Examples are to carry out pretreated with reference to the method for stipulating among the GB/T5476-1996) gets final product, and repeats no more herein.
Can handle the various inner cold waters that the generator internal part is cooled off of being used for according to hybrid resin of the present invention, for example: condensate water, demineralized water.Among the present invention, described condensate water is meant that water vapour is emitted the latent heat of vaporization when temperature is lower than saturation temperature under its relevant pressure and the aqueous water that forms; Described demineralized water is meant the finished product water that obtains through removing suspension, colloid, inorganic cation and inorganic anion processing.Hybrid resin according to the present invention is specially adapted to condensate water is handled.Preferably, the initial pH value of described condensate water is 7-8, and initial conductivity is 1-3 μ S/cm.Among the present invention, described initial pH value and initial conductivity fingering are respectively gone into the pH value and the electrical conductivity of the inner cold water before the electric generator inner cooling water circulation system.
The present invention will be described in more detail below in conjunction with embodiment.
It is that 868 pH meter is measured the pH value that following examples and Comparative Examples adopt the model that is purchased from Ao Lilong; It is that the conductivity meter of DDSJ-308A is measured electrical conductivity that employing is purchased model from thunder magnetic.
Following examples and Comparative Examples adopt condensate water available from state China Taishan electricity generating corporation, Ltd as electric generator inner cooling water, are 7.5 as the initial pH value of the condensate water of electric generator inner cooling water, and initial conductivity is 1.5 μ S/cm.
The demineralized water of the flushing ion exchange resin that uses in following examples is available from state China Taishan electricity generating corporation, Ltd, and the pH value is 6.8, and electrical conductivity is less than 0.2 μ S/cm.
The OH type ion exchange resin that following examples and Comparative Examples are used is obtained by following negative resin respectively, the H type ion exchange resin that uses is respectively by obtaining with the Xiayang resin, the Na type ion exchange resin that uses will be by being obtained transition by the H type ion exchange resin that obtains with the Xiayang resin respectively, the model of above-mentioned negative resin and positive resin and performance indications are shown in the following table 1, wherein, operating capacity is measured according to DL/T772-2001 defined terms and method.
Table 1
Preparation example 1
Adopt following method that positive Resin A is carried out preliminary treatment:
The positive Resin A that to rinse well with demineralized water is that the NaOH solution of 5 weight % soaked 8 hours with the concentration for the twice of this sun resin volume, washes to the transparent clarification of water quality with demineralized water then and does not have phenolphthalein alkalinity; Be after the HCl solution of 5 weight % soaks 8 hours with the concentration of twice that is positive resin volume again, wash to the transparent clarification of water quality, drip methyl orange indicator and be yellow and electrical conductivity≤1.0 μ S/cm with demineralized water.
Preparation example 2
It is Na type ion exchange resin that this preparation example is used for H type ion exchange resin is made the transition.
The H type ion exchange resin that employing is obtained by preparation example 1, with the concentration for the twice of resin volume is that the NaOH solution of 5 weight % soaked 24 hours, washing to the transparent clarification of water quality, no phenolphthalein alkalinity and electrical conductivity≤1.0 μ S/cm with demineralized water then, is Na type ion exchange resin thereby H type ion exchange resin is made the transition.
Preparation example 3
Adopt following method that negative resin B is carried out preliminary treatment:
The negative resin B that will rinse well with demineralized water is that the HCl solution of 5 weight % soaked 8 hours with the concentration for the twice of this negative resin volume, washes to the transparent clarification of water quality, drips methyl orange indicator and be yellow with demineralized water then; Be that the NaOH solution of 5 weight % soaked 8 hours with the concentration of twice that is the negative resin volume again, wash to the transparent clarification of water quality, no phenolphthalein alkalinity and electrical conductivity≤1.0 μ S/cm with demineralized water then.
Preparation Comparative Examples 1
Adopt the method identical that positive resin C is carried out preliminary treatment with preparation example 1.
Preparation Comparative Examples 2
Adopt the method identical with preparation example 2 that H type ion exchange resin is Na type ion exchange resin transition, different is to adopt the H type ion exchange resin by 1 acquisition of preparation Comparative Examples.
Preparation Comparative Examples 3
Adopt the method identical that negative resin D is carried out preliminary treatment with preparation example 3.
Embodiment 1
Present embodiment is used for illustrating hybrid resin of the present invention and preparation method thereof.
The OH type ion exchange resin that preparation example 3 is obtained, the Na type ion exchange resin that preparation example 2 obtains, H type ion exchange resin that preparation example 1 obtains are that 2: 0.5: 0.5 ratio mixes according to volume ratio, obtain according to hybrid resin of the present invention.In this hybrid resin, the ion-exchange group in the ion-exchange group in the OH type ion exchange resin, the Na type ion exchange resin and the mol ratio of the ion-exchange group in the H type ion exchange resin are 1: 0.42: 0.42.
Embodiment 2
Present embodiment is used for illustrating hybrid resin of the present invention and preparation method thereof.
The OH type ion exchange resin that preparation example 3 is obtained, the Na type ion exchange resin that preparation example 2 obtains, H type ion exchange resin that preparation example 1 obtains are that 2: 0.8: 0.2 ratio mixes according to volume ratio, obtain according to hybrid resin of the present invention.In this hybrid resin, the ion-exchange group in the ion-exchange group in the OH type ion exchange resin, the Na type ion exchange resin and the mol ratio of the ion-exchange group in the H type ion exchange resin are 1: 0.67: 0.17.
Embodiment 3
Present embodiment is used for illustrating hybrid resin of the present invention and preparation method thereof.
The OH type ion exchange resin that preparation example 3 is obtained, the Na type ion exchange resin that preparation example 2 obtains, H type ion exchange resin that preparation example 1 obtains are that 2: 0.85: 0.15 ratio mixes according to volume ratio, obtain hybrid resin.In this hybrid resin, the ion-exchange group in the ion-exchange group in the OH type ion exchange resin, the Na type ion exchange resin and the mol ratio of the ion-exchange group in the H type ion exchange resin are 1: 0.72: 0.13.
Embodiment 4
Present embodiment is used for illustrating hybrid resin of the present invention and preparation method thereof.
The OH type ion exchange resin that preparation example 3 is obtained, the Na type ion exchange resin that preparation example 2 obtains, H type ion exchange resin that preparation example 1 obtains are that 2: 0.15: 0.85 ratio mixes according to volume ratio, obtain hybrid resin.In this hybrid resin, the ion-exchange group in the ion-exchange group in the OH type ion exchange resin, the Na type ion exchange resin and the mol ratio of the ion-exchange group in the H type ion exchange resin are 1: 0.13: 0.72.
Embodiment 5
Present embodiment is used for illustrating hybrid resin of the present invention and preparation method thereof.
The OH type ion exchange resin that preparation example 3 is obtained, the Na type ion exchange resin that preparation example 2 obtains, H type ion exchange resin that preparation example 1 obtains are that 2: 0.9: 0.1 ratio mixes according to volume ratio, obtain hybrid resin.In this hybrid resin, the ion-exchange group in the ion-exchange group in the OH type ion exchange resin, the Na type ion exchange resin and the mol ratio of the ion-exchange group in the H type ion exchange resin are 1: 0.76: 0.084.
Comparative Examples 1
The OH type ion exchange resin that preparation example 3 is obtained, the Na type ion exchange resin that preparation example 2 obtains are to mix at 2: 1 according to volume ratio, obtain hybrid resin.In this hybrid resin, the mol ratio of the ion-exchange group in ion-exchange group in the OH type ion exchange resin and the Na type ion exchange resin is 1: 0.84.
Comparative Examples 2
The Na type ion exchange resin that the OH type ion exchange resin that obtains of preparation Comparative Examples 3, preparation Comparative Examples 2 are obtained, the H type ion exchange resin that preparation Comparative Examples 1 obtains are that 2: 0.64: 0.16 ratio mixes according to volume ratio, obtain according to hybrid resin of the present invention.In this hybrid resin, the ion-exchange group in the ion-exchange group in the OH type ion exchange resin, the Na type ion exchange resin and the mol ratio of the ion-exchange group in the H type ion exchange resin are 1: 0.68: 0.17.
Test implementation example 1
The hybrid resin of embodiment 1 preparation is seated in decides in the cold water ion-exchanger, this height of deciding the cold water ion-exchanger is 1.2 meters, and internal diameter is 50 millimeters, and the loadings of hybrid resin is 120 liters, then makes demineralized water with 3m
3The flow velocity of/h is by this hybrid resin, and the desalination electrical conductivity of water of discharging until ion-exchanger is lower than 0.8 μ S/cm.Then, should decide the cold water ion-exchanger and be connected in the electric generator inner cooling water-flow circuit, and make the inner inner cold water of discharging of generator (the pH value is in the scope of 5.5-6.5, and electrical conductivity is in the scope of 1-3 μ S/cm) with 3m
3The flow velocity of/h is by the hybrid resin in this ion-exchanger, thereby electric generator inner cooling water is handled, the circulation of electric generator inner cooling water after the processing enters generator the internal part of generator is cooled off, so electric generator inner cooling water is recycled and operation continuously, every 24 hours, use pH meter and conductivity meter to measure the pH value and the electrical conductivity of the treated inner cold water of ion-exchanger discharge, after 1 year as a result, the pH of ion-exchanger water outlet is 7.6, and electrical conductivity is 0.14 μ S/cm.
Test implementation example 2
The hybrid resin of embodiment 2 preparation is seated in decides in the cold water ion-exchanger, this height of deciding the cold water ion-exchanger is 1.2 meters, and internal diameter is 50 millimeters, and the loadings of hybrid resin is 120 liters, then makes demineralized water with 3m
3The flow velocity of/h is by this hybrid resin, and the desalination electrical conductivity of water of discharging until ion-exchanger is lower than 0.8 μ S/cm.Then, should decide the cold water ion-exchanger and be connected in the electric generator inner cooling water-flow circuit, and make the inner inner cold water of discharging of generator (the pH value is in the scope of 5.5-6.5, and electrical conductivity is in the scope of 1-3 μ S/cm) with 3m
3The flow velocity of/h is by the hybrid resin in this ion-exchanger, thereby electric generator inner cooling water is handled, the circulation of electric generator inner cooling water after the processing enters generator the internal part of generator is cooled off, so electric generator inner cooling water is recycled and operation continuously, every 24 hours, use pH meter and conductivity meter to measure the pH value and the electrical conductivity of the treated inner cold water of ion-exchanger discharge, after 1 year as a result, the pH of ion-exchanger water outlet is 8.52, and electrical conductivity is 0.27 μ S/cm.
Test implementation example 3
The hybrid resin of embodiment 3 preparation is seated in decides in the cold water ion-exchanger, this height of deciding the cold water ion-exchanger is 1.2 meters, and internal diameter is 50 millimeters, and the loadings of hybrid resin is 120 liters, then makes demineralized water with 3m
3The flow velocity of/h is by this hybrid resin, and the desalination electrical conductivity of water of discharging until ion-exchanger is lower than 0.8 μ S/cm.Then, should decide the cold water ion-exchanger and be connected in the electric generator inner cooling water-flow circuit, and make the inner inner cold water of discharging of generator (the pH value is in the scope of 5.5-6.5, and electrical conductivity is in the scope of 1-3 μ S/cm) with 3m
3The flow velocity of/h is by the hybrid resin in this ion-exchanger, thereby electric generator inner cooling water is handled, the circulation of electric generator inner cooling water after the processing enters generator the internal part of generator is cooled off, so electric generator inner cooling water is recycled and operation continuously, every 24 hours, use pH meter and conductivity meter to measure the pH value and the electrical conductivity of the treated inner cold water of ion-exchanger discharge, after 1 year as a result, the pH of ion-exchanger water outlet is 7.7-7.9, and electrical conductivity is 0.12 μ S/cm.
Test implementation example 4
The hybrid resin of embodiment 4 preparation is seated in decides in the cold water ion-exchanger, this height of deciding the cold water ion-exchanger is 1.2 meters, and internal diameter is 50 millimeters, and the loadings of hybrid resin is 120 liters, then makes demineralized water with 3m
3The flow velocity of/h is by this hybrid resin, and the desalination electrical conductivity of water of discharging until ion-exchanger is lower than 0.8 μ S/cm.Then, should decide the cold water ion-exchanger and be connected in the electric generator inner cooling water-flow circuit, and make the inner inner cold water of discharging of generator (the pH value is in the scope of 5.5-6.5, and electrical conductivity is in the scope of 1-3 μ S/cm) with 3m
3The flow velocity of/h is by the hybrid resin in this ion-exchanger, thereby electric generator inner cooling water is handled, the circulation of electric generator inner cooling water after the processing enters generator the internal part of generator is cooled off, so electric generator inner cooling water is recycled and operation continuously, every 24 hours, measure the pH value and the electrical conductivity of the treated inner cold water of ion-exchanger discharge with pH meter and conductivity meter, after 4 months as a result, the pH of ion-exchanger water outlet is 7.5, electrical conductivity is 0.13 μ S/cm, and the pH value of ion-exchanger water outlet after 5 months is reduced to and is lower than 7.0.
Test implementation example 5
The hybrid resin of embodiment 5 preparation is seated in decides in the cold water ion-exchanger, this height of deciding the cold water ion-exchanger is 1.2 meters, and internal diameter is 50 millimeters, and the loadings of hybrid resin is 120 liters, then makes demineralized water with 3m
3The flow velocity of/h is by this hybrid resin, and the desalination electrical conductivity of water of discharging until ion-exchanger is lower than 0.8 μ S/cm.Then, should decide the cold water ion-exchanger and be connected in the electric generator inner cooling water-flow circuit, and make the inner inner cold water of discharging of generator (the pH value is in the scope of 5.5-6.5, and electrical conductivity is in the scope of 1-3 μ S/cm) with 3m
3The flow velocity of/h is by the hybrid resin in this ion-exchanger, thereby electric generator inner cooling water is handled, the circulation of electric generator inner cooling water after the processing enters generator the internal part of generator is cooled off, so electric generator inner cooling water is recycled and operation continuously, every 24 hours, measure the pH value and the electrical conductivity of the treated inner cold water of ion-exchanger discharge with pH meter and conductivity meter, after 4 months as a result, the pH of ion-exchanger water outlet fluctuates between 7.8-8.1, electrical conductivity is 0.36 μ S/cm, and ion-exchanger goes out electrical conductivity of water and progressively increases to being higher than 1.5 μ S/cm after 5 months.
Test comparison example 1
The hybrid resin of Comparative Examples 1 preparation is seated in decides in the cold water ion-exchanger, this height of deciding the cold water ion-exchanger is 1.2 meters, and internal diameter is 50 millimeters, and the loadings of hybrid resin is 120 liters, then makes demineralized water with 3m
3The flow velocity of/h is by this hybrid resin, and the desalination electrical conductivity of water of discharging until ion-exchanger is lower than 0.8 μ S/cm.Then, should decide the cold water ion-exchanger and be connected in the electric generator inner cooling water-flow circuit, and make the inner inner cold water of discharging of generator (the pH value is in the scope of 5.5-6.5, and electrical conductivity is in the scope of 1-3 μ S/cm) with 3m
3The flow velocity of/h is by the hybrid resin in this ion-exchanger, thereby electric generator inner cooling water is handled, the circulation of electric generator inner cooling water after the processing enters generator the internal part of generator is cooled off, so electric generator inner cooling water is recycled and operation continuously, every 24 hours, measure the pH value and the electrical conductivity of the treated inner cold water of ion-exchanger discharge with pH meter and conductivity meter, after 3 months as a result, the pH of ion-exchanger water outlet is 8.5, electrical conductivity is 1.4 μ S/cm, and ion-exchanger goes out electrical conductivity of water and continues to be increased to and be higher than 2.0 μ S/cm after 4 months.
Test comparison example 2
The hybrid resin of Comparative Examples 2 preparation is seated in decides in the cold water ion-exchanger, this height of deciding the cold water ion-exchanger is 1.2 meters, and internal diameter is 50 millimeters, and the loadings of hybrid resin is 120 liters, then makes demineralized water with 3m
3The flow velocity of/h is by this hybrid resin, and the desalination electrical conductivity of water of discharging until ion-exchanger is lower than 0.8 μ S/cm.Then, should decide the cold water ion-exchanger and be connected in the electric generator inner cooling water-flow circuit, and make the inner inner cold water of discharging of generator (the pH value is in the scope of 5.5-6.5, and electrical conductivity is in the scope of 1-3 μ S/cm) with 3m
3The flow velocity of/h is by the hybrid resin in this ion-exchanger, thereby electric generator inner cooling water is handled, the circulation of electric generator inner cooling water after the processing enters generator the internal part of generator is cooled off, so electric generator inner cooling water is recycled and operation continuously, every 24 hours, use pH meter and conductivity meter to measure the pH value and the electrical conductivity of the treated inner cold water of ion-exchanger discharge, after 3 months as a result, the pH of ion-exchanger water outlet is 8.0, and electrical conductivity is 1.6 μ S/cm.
Table 2 has been listed the composition and the test result of test implementation example 1-5 and test comparison example 1 and 2 employed hybrid resins.
Table 2
*: the test data after 5 months;
*: the test data after 4 months.
Test implementation example 1-5 and test comparison example 1 are compared as can be seen, if hybrid resin does not contain H type ion exchange resin, and only contain OH type ion exchange resin and Na type ion exchange resin, although can significantly improve the pH value of electric generator inner cooling water, the electrical conductivity of electric generator inner cooling water can not be remained for a long time below the 1.5 μ S/cm.
With test implementation example 2 and 3 and test comparison example 2 compare as can be seen, under the essentially identical condition of other condition, OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin all adopt the hybrid resin of gel-type styrene ion exchange resin to demonstrate the pH value of better stable generator inner cold water and the performance of electrical conductivity, not only can be for a long time the pH value of electric generator inner cooling water be remained more than 7.5, but also can be for a long time the electrical conductivity of electric generator inner cooling water be remained below the 0.3 μ S/cm.Yet, when the OH type ion exchange resin in the hybrid resin, Na type ion exchange resin and H type ion exchange resin are macroreticular ion exchange resin, can not be for a long time the electrical conductivity of electric generator inner cooling water be remained below the 1.5 μ S/cm.
Claims (12)
1. hybrid resin, it is characterized in that, this hybrid resin contains OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, and described OH type ion exchange resin, Na type ion exchange resin and the H type ion exchange resin gel-type ion-exchange resin of respectively doing for oneself.
2. hybrid resin according to claim 1, wherein, the mol ratio of the ion-exchange group in the described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is 1: 0.1-0.8: 0.08-0.75.
3. hybrid resin according to claim 2, wherein, the mol ratio of the ion-exchange group in the described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is 1: 0.4-0.75: 0.1-0.45.
4. hybrid resin according to claim 3, wherein, the mol ratio of the ion-exchange group in the described OH type ion exchange resin, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin is 1: 0.65-0.75: 0.1-0.2.
5. hybrid resin according to claim 1, wherein, described gel-type ion-exchange resin is the polystyrene gel-type ion-exchange resin.
6. according to any described hybrid resin among the claim 2-4, wherein, the operating capacity of described OH type ion exchange resin be the 450-600 mM/liter, the operating capacity of the operating capacity of described Na type ion exchange resin and H type ion exchange resin respectively do for oneself the 950-1010 mM/liter.
7. according to any described hybrid resin among the claim 1-4, wherein, the ion-exchange group of described OH type ion exchange resin is-N (CH
3)
3OH, the ion-exchange group of described Na type ion exchange resin is-SO
3Na, the ion-exchange group of described H type ion exchange resin is-SO
3The H group.
8. method for preparing the described hybrid resin of claim 1, it is characterized in that, this method comprises mixes OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin, and described OH type ion exchange resin, Na type ion exchange resin and the H type ion exchange resin gel-type ion-exchange resin of respectively doing for oneself.
9. method according to claim 8, wherein, the volume ratio of the operating capacity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin and described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin makes that the mol ratio of ion-exchange group, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin in the described OH type ion exchange resin is 1: 0.1-0.8: 0.08-0.75.
10. method according to claim 9, wherein, the volume ratio of the operating capacity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin and described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin makes that the mol ratio of ion-exchange group, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin in the described OH type ion exchange resin is 1: 0.4-0.75: 0.1-0.45.
11. method according to claim 10, wherein, the volume ratio of the operating capacity of described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin and described OH type ion exchange resin, Na type ion exchange resin and H type ion exchange resin makes that the mol ratio of ion-exchange group, the ion-exchange group in the Na type ion exchange resin and the ion-exchange group in the H type ion exchange resin in the described OH type ion exchange resin is 1: 0.65-0.75: 0.1-0.2.
12. according to any described method among the claim 9-11, wherein, the operating capacity of described OH type ion exchange resin be the 450-600 mM/liter, the operating capacity of the operating capacity of described Na type ion exchange resin and H type ion exchange resin respectively do for oneself the 950-1010 mM/liter.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761022A (en) * | 2015-03-23 | 2015-07-08 | 神华集团有限责任公司 | Method for treating cold water in generator |
| CN106044946A (en) * | 2016-06-29 | 2016-10-26 | 佛山市云米电器科技有限公司 | Filter element capable of adjusting pH value of effluent |
| CN112573615A (en) * | 2019-09-29 | 2021-03-30 | 西安正清和环境科技有限公司 | Development process of nuclear-grade internal cooling water resin |
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| CN1587086A (en) * | 2004-08-17 | 2005-03-02 | 江西省电力试验研究院 | Weak alkaline circulation water treating and anti-corrosion method for water cooling generator static wire stick |
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| CN1587086A (en) * | 2004-08-17 | 2005-03-02 | 江西省电力试验研究院 | Weak alkaline circulation water treating and anti-corrosion method for water cooling generator static wire stick |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104761022A (en) * | 2015-03-23 | 2015-07-08 | 神华集团有限责任公司 | Method for treating cold water in generator |
| CN104761022B (en) * | 2015-03-23 | 2016-11-02 | 神华集团有限责任公司 | A kind of method processing electric generator inner cooling water |
| CN106044946A (en) * | 2016-06-29 | 2016-10-26 | 佛山市云米电器科技有限公司 | Filter element capable of adjusting pH value of effluent |
| CN112573615A (en) * | 2019-09-29 | 2021-03-30 | 西安正清和环境科技有限公司 | Development process of nuclear-grade internal cooling water resin |
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